Process for the production of living (co)polymers and use of the (co)polymers

ABSTRACT

The purpose of the present invention is to provide polymerization catalyst which can produce quite efficiently (co)polymer having number average molecular weight and number of molecules which are accurately controlled in producing method of (co)polymer by the polymerization of polar unsaturated compound, and provide living polymerized (co)polymer obtained according to the producing method. For the purpose, polymerization catalyst composition which comprises the composition comprising organic oxysalt compound and hydroxycarbonyl compound having at least both an alcoholic hydroxyl group and a carbonyl group in the same molecule is provided and the polar unsaturated compound is polymerized by using the polymerization catalyst composition. The composition containing the obtained (co)polymer were able to provide thermosetting powder coating composition having particularly excellent characteristics.

TECHNICAL FIELD

[0001] The invention described herein relates to a method of producing aliving polymerized (co)polymer by polymerizing a polar unsaturatedcompound using an organic oxysalt compound as catalyst. These polymerand copolymer are very important ones as raw materials of polymermaterials and functional polymers.

[0002] The invention relates particularly to compositions ofthermosetting powder coatings, more particularly, to the compositions ofthermosetting powder coatings having excellent storage stability(blocking resistance), external appearance (surface flatness,brightness, and transparency), physical property (hardness, scratchresistance, and recoating property), and chemical property (weatherresistance, acid resistance, and solvent resistance) and to thecompositions of thermosetting powder coatings which can provide bakedcoating films particularly suitable for use of coating vehicles.

[0003] Background Art

[0004] Enormous number of researches have been made with regard to thepolymerization of polar unsaturated compounds for many years. Amongthem, recently a number of researches on living polymerization catalystshave been conducted aiming at producing polymers having less narrowmolecular weight distribution by controlling optionally and rigorouslythe molecular weight of polymers to be obtained and variouspolymerization catalyst systems have been developed which have theproperty of living radical polymerization, living anion or livingcoordination anion polymerization (for example, living radicalpolymerization catalysts: Koubunshi, vol.48, (7) pp 498-501 (1999);living anion and living coordination anion polymerization catalysts:Shin koubunshi Jikkengaku vol.2“Shin Koubunshi noGousei•Hannou(1)—Fukakei koubunshi no Gousei—” pp 165-196, KyourituShuppan Kabushikigaisha (1995)).

[0005] Many effective living polymerization catalysts have beendeveloped and from the view point of “the number of produced polymermolecules corresponding to the number of molecules of polymerizationcatalyst used” in most cases only one polymer molecule is obtained fromone molecule of polymerization catalyst, that is, stoichiometricpolymerization is observed. This stoichiometric living polymerizationrequires one molecule of the polymerization catalyst to produce onepolymer molecule which is not an efficient and effective method ofproduction in the light of industrially practical use. On the otherhand, in catalytic living polymerization wherein plural number ofpolymer molecules are produced by one molecule of polymerizationcatalyst it is possible to avoid or simplify the complicated processesof separating catalysts and control unfavorable effects on the polymerproperty to a minimum by reducing drastically the concentration ofcatalyst components remaining in the polymer produced. Furthermore, thismethod is a really practical one from the view point of reducingenvironmental load and catalyst cost. Actually, the polymerizationcatalyst systems of polar unsaturated compounds which have beenpracticed are composed of very small amount of radical generating agents(which mean the catalysts described herein) and a large amount of chaintransfer agents. Although the polymerization does not proceed likeliving one, it produces very efficiently the number of polymer moleculescomparable to the number of molecules of the chain transfer agents fromone radical molecule.

[0006] The known examples of the catalytic living polymerization ofpolar unsaturated compounds are {circumflex over (1)} polymerization ofmethacrylate using alkali metal alkoxide as catalyst and alcohol aschain transfer agent (S. N. Lewis et al., Progress in Organic Coating12, 1-26 (1984)) and {circumflex over (2)} polymerization ofmethacrylate and acrylate using quaternary ammonium salt or Lewis acidas catalyst and silyl ketene ketal as chain transfer agent (O. W.Websteret al., J.Am.Chem.Soc., 105, 5703 (1983) or Shin koubunshi Jikkengakuvol.2“Shin Koubunshi no Gousei•Hannou(1)—Fukakei koubunshi no Gousei—”pp 365-386, Kyouritu Shuppan Kabushikigaisha (1995)). However, themethod {circumflex over (1)} is a good polymerization method forproducing oligomers having average molecular weight of 500-3000 butcannot produce oligomers having average molecular weight greater than orequal to 3000 or (co)polymers by controlling their molecular weight andmolecular weight distribution precisely. Furthermore, since this methoduses alcohol as both chain transfer agent and polymerization solvent,transesterification proceeds simultaneously with polymerization.Therefore, there is a drawback that this method cannot apply to themonomers when the transesterification causes some problems. The method{circumflex over (2)} has not been practiced yet, because silyl keteneketal is expensive and unstable and there are some problems in theproduction method.

[0007] As an important use utilizing the property of the (co)polymerwhich is obtained by the method of the present invention there arepowder coatings and prior arts relating to them which will be explainedin the following:

[0008] Solvent type coating materials have usually been used forpainting bodies and those which satisfy various requirements have beendeveloped and used in order to be utilized in the field of automobileswhere rigorous quality specification is required.

[0009] Recently in the technical field of coating materials, shift tousing powder coatings have been expected in place of solvent typecoating materials in the light of local or global environmentconservation, environment improvement of health and safety at work,prevention of fire and explosion, and resource conservation. And fromthe historical and social requests, as expectation for high functionperformance and diversification of powder coatings have been increased,high paint film performance (for example, weather resistance, acid rainresistance, and scratch resistance) of powder coatings comparable tosolvent type coating materials have been requested. However, in spite ofsevere requests for paint film performance, powder coatings whichsatisfy these requests have not necessarily been placed on the market.

[0010] As specific examples of the conventional types of powder coatingsthere are those of epoxy resin and polyester resin. However, thesecoatings have not only problems in weather resistance but also inresistance against the acid rain which has recently become a particularproblem and, therefore, these problems were regarded as critical in thefield of painting automobile bodies.

[0011] For the purpose of eliminating the drawback, acrylic powdercoatings was proposed in JP-B-48-38617 and remarkable improvement inweather resistance has been realized. Since then many researches havebeen made on the acrylic powder coatings, however, these acrylic powdercoatings have not satisfied sufficiently external appearance property,physical property, chemical property, storage property, and particularlysurface flatness and blocking resistance simultaneously. Reduction inmelt viscosity is the most effective to improve the surface flatness,however, in order to reduce the melt viscosity it was necessary to lowera glass transition temperature by which method it was impossible tosatisfy both the surface flatness and the blocking resistance.

[0012] For the purpose of providing the surface flatness and theblocking resistance simultaneously, thermosetting powder coatingscomposition (WO96/03464) is proposed which uses acrylic (co)polymerhaving narrow molecular weight distribution. It is surely possible tohave the surface flatness and the blocking resistance simultaneously bynarrowing the molecular weight distribution. However, according to themethod of living polymerization which is described as an example ofproducing method of the acrylic (co)polymer used therein, due to theinsufficient recoating property (adhesion property with top coatings atrepainting and maintenance) the powder coatings, particularly as topcoatings, did not show the effectiveness sufficiently. As anotherexample of the production, an acrylic (co)polymer having the prescribedmolecular weight distribution is shown by fractionating the acrylic(co)polymer obtained by radical polymerization method. However, in thismethod the proportion of the (co)polymer to be obtained as a target islow and a process of the fractionation is required, therefore, themethod is costly and not practical. Researches on various livingpolymerization methods have been conducted for the purpose of narrowingthe molecular weight distribution of acrylic (co)polymer, however,because of coloring, stench, and high cost of the acrylic (co)polymersproduced there have not been the method of producing acrylic(co)polymers and thermosetting powder coatings which can favorably beapplied to painting automobile bodies and parts for vehicles such asautomobiles, particularly, painting of top coatings.

[0013] The purpose of the present invention is to provide a method ofproducing living (co)polymers effectively and efficiently by catalyticliving polymerization of polar unsaturated compounds when (co)polymersare produced by the polymerization of polar unsaturated compounds.

[0014] Another purpose of the present invention is to providethermosetting powder coating compositions (for example acrylicthermosetting powder coating compositions) having storage stability,external appearance property, physical property, and chemical propertyin the light of the problems described above; particularly to providethermosetting powder coating compositions (for example acrylicthermosetting powder coating compositions) which are applied favorablyto the painting automobile bodies and parts for vehicles such asautomobiles (aluminum wheels, windshield wipers, pillars, door handles,fenders, bonnets, air spoilers, stabilizers, and front grilles),particularly, to the painting of top coatings.

DISCLOSURE OF THE INVENTION

[0015] As a result of the extensive and through researches to achievethe purposes described above, the inventors of the present inventionhave completed the present invention by finding out that by a method ofpolymerization of polar unsaturated compounds using an organic oxysaltcompound as catalyst in the presence of a hydroxycarbonyl compoundhaving at least both an alcoholic hydroxyl group and a carbonyl group inthe same molecule the polymerization has the property of stoichiometricor catalytic living polymerization and it is possible to controlprecisely not only the average molecular weight of the (co)polymerproduced but also the number of the molecules of the (co)polymer.

[0016] That is, the present invention is a method of producing a livingpolymerized (co)polymer comprising polymerization of polar unsaturatedcompound using organic oxysalt compound as catalyst in the presence of ahydroxycarbonyl compound having at least both an alcoholic hydroxylgroup and a carbonyl group in the same molecule when producing the(co)polymer by (co)polymerization of polar unsaturated compounds usingoxysalt compound as catalyst.

[0017] Furthermore, as a result of more extensive and through researchesto resolve the problems of the prior arts as described above, theinventors found out the knowledge that by using the (co)polymer(A) asdescribed above it is possible to provide a thermosetting powder coatingcomposition having excellent storage stability, external appearance,physical property, and chemical property (for example, an acrylicthermosetting powder coating composition) and completed the presentinvention.

[0018] The present invention is specified by items as described in thefollowing [1]-[17]:

[0019] [1] A method of producing a living polymerized (co)polymer whichmethod comprises polymerization of polar unsaturated compound in thepresence of a hydroxycarbonyl compound having at least both an alcoholichydroxyl group and a carbonyl group in the same molecule using anorganic oxysalt compound as catalyst.

[0020] [2] The method as described in [1], wherein a cation forming theorganic oxysalt compound is an alkali metal cation, a tetraalkylammoniumcation, a trialkylsulfonium cation, a tetraarylphosphonium cation, ahexaarylphosphoranilidene ammonium cation, or atetrakis{tris(dialkylamino)phosphoranilideneamino}phosp honium cation.

[0021] [3] The method as described in [1], wherein the cation formingthe organic oxysalt compound is a tetraalkylammonium cation, atetraarylphosphonium cation, or a hexaarylphosphoranilidene ammoniumcation.

[0022] [4] The method as described in any one of [1] to [3], wherein ananion forming the organic oxysalt compound is an organic oxyanionderived from a monohydric alcohol, an organic oxyanion derived from amonocarboxylate, or an organic oxyanion derived from a polycarboxylate.

[0023] [5] The method as described in any one of [1] to [3], wherein ananion forming the organic oxysalt compound is an organic oxyanionderived from a monohydric alcohol.

[0024] [6] The method as described in any one of [1] to [5], wherein thehydroxycarbonyl compound is an α-hydroxyketone or anα-hydroxycarboxylate.

[0025] [7] The method as described in any one of [1] to [6], wherein thepolar unsaturated compound is a chemical compound having both a polarfunctional group selected from carbonyl, cyano, or pyridyl groups, andan unsaturated group in the same molecule and, in addition, thefunctional group and the unsaturated group form a direct or indirectconjugated system.

[0026] [8] The method as described in any one of [1] to [6], wherein thepolar unsaturated compound is a (meth)acrylate, a (meth)acrylonitrile, a(meth)acrylamide, a vinylpiridine, a N-substitued maleimide, avinylketone, or a styrene derivative.

[0027] [9] The method as described in any one of [1] to [6], wherein thepolar unsaturated compound is a monoester between a monohydric alcoholand acrylic acid or methacrylic acid, a monoester between acrylic acidor methacrylic acid and a dihydric alcohol one end of which is protectedby ether linkage, a polyester formed by esterification between acrylicacid or methacrylic acid and all of the hydroxyl groups of thepolyhydric alcohol, having two or more hydroxyl groups, anacrylonitrile, a methacrylonitrile, a N,N-disubstitutedmono(meth)acrylamide, a pyridine substituted by vinyl or isopropenylgroup, a N-aromatic substituted maleimde or a vinylketone.

[0028] [10] The method as described in any one of [1] to [9], wherein anactive hydrogen compound is used as chain transfer agent.

[0029] [11] The method as described in any one of [1] to [9], whereinthe chain transfer agent is a monocarboxylate,a polycarboxylate, amonohydric alcohol, a polyhydric alcohol, a monothiol, a(co)poly(alkyleneoxide) having an active hydrogen at its end and/or inits backbone chain, a (co)poly{(meth)acrylate}, a(co)poly{(meth)acrylonitrile}, a (co)poly{(meth)acrylamide}, a(co)poly(vinylpyridine), a (co)poly(N-substitued maleimide), a(co)poly(vinylketone), or a (co)poly(styrene derivative).

[0030] [12] The method as described in any one of [1] to [11], whereinthe copolymer is produced by using at least two or more of the polarunsaturated compounds together.

[0031] [13] A thermosetting powder coating composition comprising;

[0032] a living polymerized (co)polymer (A) obtained by the method asdescribed in any one of [1] to [12] and

[0033] a curing agent composition component(B) which can cure said(co)polymer.

[0034] [14] The thermosetting powder coating composition as described in[13], wherein the (co)polymer(A) comprises an epoxy group.

[0035] [15] The thermosetting powder coating composition as described in[13] or [14], wherein the (co)polymer(A) has a glass transitiontemperature of 10° C.-100° C.

[0036] [16] The thermosetting powder coating composition as described inany one of [13] or [15], wherein the curing agent compositioncomponent(B) which can cure the (co)polymer comprising;

[0037] (b-1) a polycarboxylic acid and/or

[0038] (b-2) a polycarboxylic acid anhydride.

[0039] [17] The thermosetting powder coating composition as described inany one of [13] to [16] wherein the thermosetting powder coatingcomposition is for use as top coating of automobiles.

BEST MODES FOR CARRYING OUT THE INVENTION

[0040] The present invention relates to a method of producing a livingpolymerized (co)polymer by the (co)polymerization of a polar unsaturatedcompound using organic oxysalt compound as catalyst in the presence ofhydroxycarbonyl compound having at least both an alcoholic hydroxylgroup and a carbonyl group in the same molecule.

[0041] The organic oxysalt compound used in the present invention is asalt compound composed of an anion part having univalent organicoxyanion structure expressed by the formation of bonding an organicgroup to an oxygen atom as total structure or partial one and a cationpart which is formed by a metal cation or an organic cation which canneutralize the anion in terms of electric charge.

[0042] As metal cations among the ones forming these organic oxysaltcompounds any metal cations may be used as far as they do not hinder thepurposes of the present invention, and as specific examples of suchcations, there are cations of alkali metals or those of alkaline earthmetals. As organic cations any cations may be used as far as they do nothinder the purposes of the present invention and as specific examples ofsuch cations, there are quaternary ammonium cations, tertiary sulfoniumcations, quaternary phosphonium cations, phosphoranilidene ammoniumcations, or phosphoranilideneaminophosphonium cations.

[0043] As quaternary ammonium cations among these organic cations, thereare, for example, ammonium ions which have nitrogen atom bonding to fourhydrocarbon groups such as tetramethylammonium ion, tetraethylammoniumion, tetrabutylammonium ion, tetrahexylammonium ion,tricyclohexylmethylammonium ion, N,N-dimethylpiperidinium ion, ortrimethylphenylammonium ion, or nitrogenous heterocyclic ammonium ionssuch as N-methylpyridinium ion, N-tert-butylpyridinium ion,N-methylpyrrolidinium ion, N,N′-dimethylimidazolinium ion, orN,N′-diisopropylimidazolinium ion.

[0044] As tertiary sulfonium cations there are, for example,trimethylsulfonium cation, triethylsulfonium cation,triisopropylsulfonium cation, tributylsulfonium cation, orphenyldimethylsulfonium cation.

[0045] As quaternary phosphonium cations, there are, for example,tetramethylphosphonium cation, tetraethylphosphonium cation,tetrabutylphosphonium cation, tetrahexylphosphonium cation,tetracyclohexylphosphonium cation, tetraphenylphosphonium cation,tetramethoxyphenylphosphonium cation, tetranaphthylphosphonium cation.

[0046] As phosphoranilidene ammonium cations, there are, for example,hexamethylphosphoranilidene ammonium cation, hexaethylphosphoranilideneammonium cation, hexapropylphosphoranilidene ammonium cation,hexabutylphosphoranilidene ammonium cation, hexaphenylphosphoranilideneammonium cation, or hexanaphthylphosphoranilidene ammonium cation.

[0047] As phosphoranilideneaminophosphonium cations, there are, forexample, tris(dimethylamino){tris(dimethylamino)phosphoranilideneamino}phosphonium cation,tris(diethylamino){tris(diethylamino)phosphoranilidenea mino}phosphoniumcation, bis(dimethylamino)bis{tris(dimethylamino)phosphoranilideneamino}phosphonium cation,dimethylaminotris{tris(dimethylamino)phosphoranilidenea mino}phosphoniumcation, tetrakis{tris(dimethylamino)phosphoranilideneamino}phos phoniumcation, tetrakis{tris(morpholino)phosphoranilideneamino}phospho niumcation, or tetrakis{tris(piperazino)phosphoranilideneamino}phospho niumcation.

[0048] Among cations which form the organic oxysalt compounds,preferable ones are, for example, alkali metal cations such as lithiumcation, sodium cation, potassium cation, cesium cation, or rubidiumcation, and tetraalkylammonium ions such as tetramethylammonium ion,tetraethylammonium ion, tetrabutylammonium ion, or tetrahexylammoniumion, and trialkylsulphonium cations such as trimethylsulphonium cation,triethylsulphonium cation, triisopropylsulphonium cation, ortributylsulphonium cation, and tetraarylphosphonium cations such astetraphenylphosphonium cation, tetramethoxyphenylphosphonium cation, ortetranaphthylphosphonium cation, and hexaarylphosphoranilidene ammoniumcations such as hexaphenylphosphoranilidene ammonium cation orhexanaphthylphosphoranilidene ammonium cation, ortetrakis{tris(dialkylamino)phosphoranilideneamino}phosp honium cationssuch as tetrakis{tris(dimethylamino)phosphoranilideneamino}phos phoniumcation, tetrakis{tris(molpholino)phosphoranilideneamino}phospho niumcation, or tetrakis{tris(piperazino)phosphoranilideneamino}phospho niumcation; and more preferable cations are tetraalkylammonium cations,tetraarylphosphonium cations, or hexaarylphosphoranilidene ammoniumcations.

[0049] On the other hand, as anions which form the organic oxysaltcompounds in the present invention, any organic anions may be used asfar as they do not hinder the purpose of the invention. As specificexamples, there are organic oxyanions of monohydric alcohols which arederived by leaving active hydrogen atoms as protons on the alcoholichydroxyl groups, for example, methanol, ethanol, n-propanol,isopropanol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol,isopentyl alcohol, tert-pentyl alcohol, n-octyl alcohol, lauryl alcohol,cetyl alcohol, cyclopentanol, cyclohexanol, allyl alcohol, crotylalcohol, methylvinylcarbinol, benzyl alcohol, 1-phenylethyl alcohol,triphenylcarbinol, cinnamyl alcohol, or perfluoro-tert-butyl alcohol,and organic oxyanions of polyhydric alcohols which are derived byleaving active hydrogen atoms as protons on the alcoholic hydroxylgroups, for example, ethylene glycol, propylene glycol, diethyleneglycol, dipropylene glycol, 1,3-propandiol, 1,3-butanediol,1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanediol, trimethylolpropane,glycerin, diglycerin, pentaerythritol, or dipentaerythritol, and organicoxyanions of monocaboxylates which are derived by leaving activehydrogen atoms as protons existing on α-carbons, for example, methylacetate, ethyl acetate, cyclohexyl propionate, isopropyl butyrate,methyl isobutyrate, t-butyl isobutyrate, hexyl caproate, butyl laurate,methyl stearate, ethyl oleate, methyl phenyl acetate, methylcyclohexanecarboxylate, 1,2-bis(2-propylcarbonyloxy)ethane, or1,2,3-tris(2-propylcarbonyloxy)propane, and organic oxyanions ofpolycaboxylates which are derived by leaving active hydrogen atoms asprotons existing on a-carbons in carbonyl group, for example, dimethylmalonate, dimethyl methylmalonate, diethyl succinate, butyl2,3--dimetylsuccinate, methyl adipate, ethyl suberate, methylbutanetetracarboxylate, 1,2-bis(2-methoxycabonylethoxy)ethane,1,2-bis(2-ethoxycarbonylpropoxy)ethane,1,2-bis(2-ethoxycarbonylpropylmercapto)ethane,N,N,N′,N′-tetrakis(2-butoxycarbonylpropyl)ethylenediamine or oligo orpoly(methyl methacrylate) having average molecular weight of 200 to1,000,000, and organic oxyanions of ketocaboxylates which are derived byleaving active hydrogen atoms as protons existing on α-carbons incarbonyl groups, for example, ethyl acetoacetate, cyclopentylacetoacetate, methyl carbamoylacetate, ethyl2-cyclohexylcarbonylacetate, or butyl benzoylacetate.

[0050] Among these anions, preferable anions are organic oxyanionsderived from monohydryic alcohols, those derived from monocarboxylates,or those derived from polycarboxylates and more preferable ones areorganic oxyanions derived from monohydric alcohols.

[0051] The organic oxysalt compounds used in the present invention areformed by the combination of these organic oxyanions and metal cationsor organic cations described above, and the combination of two or morethan two kinds of the organic oxysalt compounds may be used.

[0052] Quantity of the organic oxysalt can be determined optionallydepending on aimed molecular weight of (co)polymer to be produced andcan be determined by calculating formulas (1) or (2) described later.

[0053] The hydroxycarbonyl compounds used in the present invention haveat least both an alcoholic hydroxyl group and a carbonyl group in thesame molecule, and specific examples of these compounds areα-hydroxyketones, for example, 1-hydroxy-1,1-dimethyl-2-propanone,1-hydroxy-1,1-dimethyl-3, 3,3-trimethyl-2-propanone,α-hydroxy-α-methylethylcyclohexcylketone,α-hydroxy-α-methyl-α′-methylcyclohexcylketone,α-hydroxydicyclohexcylketone, α-hydroxy-α′-methyldicyclohexcylketone,α-hydroxy-α-methylphenylketone, α-hydroxycyclohexcylphenylketone,benzoin, α-hydroxy-α, α-diphenylacetophenone, and α-hydroxycarboxylates,for example, ethylα-hydroxyacetate, methyl lactate, cyclohexcyl lactate,ethylα-hydroxyacetate, butylα-hydroxy-iso-butyrate,methylα-hydroxy-α-phenylacetate, ethylα-hydroxy-α, α-diphenylacetate,and α-hydroxy-N,N-disubstitutedamides, for example,α-hydroxy-N,N-dimethylacetamide, α-hydroxy-α,α-dimethyl-N,N-dimethylacetamide, α-hydroxy-α,α-diphenyl-N,N-dimethylacetamide, α-hydroxy-N,N-diethylpropionamide orα-hydroxy-α-methyl-N,N-diethylpropionamide. As other examples, anyhydroxyketone compounds may be used as far as they do not hinder thepurposes of the present invention and two or more than two kinds ofhydroxyketone compounds described above may be used together.

[0054] Among these compounds, preferable α-hydroxyketones are, forexample, 1-hydroxy-1,1-dimethyl-2-propanone, 1-hydroxy-1,1-dimethyl-3,3,3-trimethyl-2-propanone, α-hydroxy-α-methylethylcyclohexcylketone,α-hydroxy-α-methylethyl-α′-methylcyclohexcylketone,α-hydroxydicyclohexcylketone, α-hydroxy-α′-methyldicyclohexcylketone,α-hydroxy-α-methylphenylketone, α-hydroxycyclohexcylphenylketone,benzoin, α-hydroxy-α, α-diphenylacetophenone, and α-hydroxycarboxylates,for example, ethylα-hydroxyacetate, methyl lactate, cyclohexcyl lactate,ethylα-hydroxybutyrate, butyl α-hydroxyisobutyrate,methylα-hydroxy-α-phenylacetate, ethylα-hydroxy-α,α-diphenylacetate, andmore preferable α-hydroxyketones are, for example, α-hydroxyacetone,1-hydroxy-1,1-dimethyl-2-propanone, 1-hydroxy-1,1-dimethyl-3,3,3-trimethyl-2-propanone, α-hydroxy-α-methylethylcyclohexcylketone,α-hydroxy-α-methylethyl-α′-methylcyclohexcylketone,α-hydroxydicyclohexcylketone, α-hydroxy-α′-methyldicyclohexcylketone,α-hydroxy-α-methylethylphenylketone, α-hydroxycyclohexcylphenylketone,benzoin, α-hydroxy-α, α-diphenylacetophenone.

[0055] Quantity of the hydroxyketone to be used is usually more than0.05 moles, preferably 0.80 to 1.20 moles, more preferably 0.95 to 1.05mole to one mole of the organic oxysalt compound. Excess quantity of thehydroxyketone acts as a chain transfer agent.

[0056] In the present invention it is possible to achieve stoichiometricand catalytic living polymerization of polar unsaturated compound usingorganic oxysalt compound as catalyst in the presence of hydroxycarbonylcompounds having at least both an alcoholic hydroxyl group and acarbonyl group in the same molecule. More specifically, {circumflex over(1)} the stoichiometric living polymerization can be performed bycontacting organic oxysalt compounds with polar unsaturated compoundsfor polymerization in the presence of hydroxycarbonyl compounds havingat least both an alcoholic hydroxyl group and a carbonyl group in thesame molecule, and {circumflex over (2)}the catalytic livingpolymerization can further be carried out using active hydrogen compoundas chain transfer agent. Since in both cases the polymerization proceedslivingly, the average molecular weight and the number of the moleculesof the (co)polymer to be produced may be calculated and predictedapproximately by the following calculation formulas (1) or (2) whereinMwa indicates the molecular weight of the oxyanion in the organicoxysalt compound; Mb indicates the number of moles of polar unsaturatedcompound; Ma indicates the number of moles of the said oxyanion; MWbindicates the molecular weight of the polar unsaturated compound; MWcindicates the molecular weight of the chain transfer agent; Mc indicatesthe number of moles of the chain transfer agent.

[0057] {circumflex over (1)} (co)polymer obtained by stoichiometricliving polymerization:

<number average molecular weight>≈Mwa+(Mb/Ma)×MWb

<number of molecules of the produced (co)polymer>≈(number of the saidorganic oxysalt compound)  (1)

[0058] {circumflex over (2)} (co)polymer obtained by catalytic livingpolymerization:

<number average molecular weight>≈(MWa×Ma+MWc×Mc+Mb×MWb)/(Ma+Mc)

<number of molecules of the produced (co)polymer>≈(number of moleculesof the said organic oxysalt compound+number of the molecule of the chaintransfer agent). (2)

[0059] As can be seen from the calculation formulas described above,according to the methods of the present invention it is possible toproduce a (co)polymer having optionally controlled number averagemolecular weight and number of the produced (co)polymer by adjustingmolecular weight and number of moles of the organic oxysalt compound,polar unsaturated compound or chain transfer agent, i.e., activehydrogen compound to be used.

[0060] In the method of the present invention, the unsaturated group isunsaturated gruop having one to four valences derived from alkene andthe polar unsaturated compound is the chemical compound having polarfunctional group and unsaturated group in the same molecule selectedfrom the group consisting of carbonyl, cyano, and pyridyl, and, inaddition, the functional group and the unsaturated group form a director indirect conjugated systems. These chemical compounds are, forexample, (1) (meth)acrylates, (2) (meth)acrylonitriles, (3)(meth)acrylamides, (4) vinylpyridines, (5) N-substituted maleimides, (6)vinylketones, or styrene derivatives. Any polar unsaturated compoundsmay be used as far as they can achieve anionic polymerization by themethod of the present invention.

[0061] As specific examples, (1) (meth)acrylates are esters of acrylicacid or methacrylic acid. These esters are, for example:

[0062] (1)-{circumflex over (1)} monoesters formed by esterificationbetween monohydric alcohols and acrylic acid or methacryic acid: theseesters are, for example, methyl acrylate, methyl methacrylate, ethylacrylate, propyl methacrylate, butyl acrylate, 2-ethylhexylmethacrylate, lauryl acrylate, stearyl methacrylate,1,1,1,3,3,3-hexafluoroisopropyl acrylate,1,1,1,3,3,3-hexafluoroisopropyl methacrylate, 2,2,2-trifluoroethylacrylate, 2,2,2-trifluoroethyl methacrylate,1H,1H,2H,2H-heptadecafluorodecyl acrylate, allyl acrylate, allylmethacrylate, cyclohexyl methacrylate, isophonyl acrylate, glycidylacrylate, gycidyl methacrylate, tetrahydrofurfuryl acrylate, benzylacrylate or β-phenylethyl methacrylate.

[0063] (1)-{circumflex over (2)} Monoesters formed by esterificationbetween dihydric alcohols whose one end is protected by an ether bondand acrylic acid or methacrylic acid: these esters are, for example,2-methoxyethyl acrylate, 2-ethoxyethyl methacrylate, 2-phenoxyethylacrylate, 2-dicyclopentenyloxyethyl acrylate, 1-methoxy-2-propylmethacrylate, 3-methoxypropyl acrylate, 4-ethoxybutyl methacrylate,6-methoxyhexamethyl acrylate, methoxydiethylene glycol arylate,phenoxydipropylene glycol methacrylate, ethoxytripropylene glycolmethacrylate, ethoxypolyethylene glycol acrylate, ormethoxypolypropylene glycol methacrylate.

[0064] (1)-{circumflex over (3)} Polyesters formed by eserificationbetween acrylic acid or methacrylic acid and all of the hydroxyl groupsof dihydric alcohols and polyhydric alcohols having more than twohydroxyl groups: these esters are, for example, ethylene glycoldiacrylate, ethylene glycol dimethacrylate, propylene glycol diacrylate,propylene glycol dimethacrylate, 1,3-propanediol dimethacrylate,1,4-butanediol diacrylate, 1,6-hexanediol dimethacrylate, neopentylglycol diacrylate, neopentyl glycol dimethacrylate, diethylene glycoldiacrylate, dipropylene glycol dimethacrylate, triethylene glycoldimethacrylate, tripropylene glycol diacrylate, polyethylene glycoldiacrylate, polypropylene glycol diacrylate, or polypropylene glycoldimethacrylate, and, in addition, glycerin triacrylate, glycerintrimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritolhexaacrylate, trimethylolpropane triacrylate, poly(ethylene oxide)trioltriacrylate, poly(propylene oxide)triol triacrylate, or poly(propyleneoxide)triol trimethacrylate.

[0065] (1)-{circumflex over (4)} Esters formed by esterification betweenalcohols containing ester bonds and acrylic acid or methacrylic acid:these esters are, for example, 2-benzoyloxyethyl acrylate,2-benzoyloxyethyl methacrylate, 2-acetyloxy acrylate,5-tetrahydrofurfuryloxycarbonylpentyl acrylate,5-tetrahydrofurfuryloxycarbonylpentyl methacrylate,2,2,6,6-tetramethyl-4-oxy-5-oxa-heptane-1,7-diyl-diacrylate.

[0066] (1)-{circumflex over (5)} Esters formed by esterification betweenalcohols having cycloacetal bond and acrylic acid or methacrylic acid:these esters are, for example, 2-t-butyl-1,3-dioxycyclopentane-2′-ilmethacrylate, or2-t-butyl-5-ethyl-5-vinylcarbonyloxymethyl-1,3-dioxycyclohexane-2′(2)-ilacrylate.

[0067] (1)-{circumflex over (6)} Esters formed by esterification betweenoxysuccinimide and acrylic acid or methacrylic acid: these esters are,for example, N-oxysuccinimide acrylate or N-oxysuccinimide methacrylate.

[0068] (1)-{circumflex over (7)} Esters formed by esterification betweenalcohols having secondary amino group and acrylic acid or methacrylicacid: these esters are, for example, 2-dimethylaminoethyl acrylate or2-ethylpropylaminoethyl methacrylate.

[0069] (1)-{circumflex over (8)} Esters formed by esterification betweenalcohols having cyano group and acrylic acid or methacrylic acid: theseesters are, for example, 2-cyanoethyl acrylate or 2-cyanopropylmethacrylate.

[0070] (2) (Meth)acrylonitriles are, for example, acrylonitrile ormethacrylonitrile.

[0071] (3) (Meth)acrylamides are, for example, acrylamide,N-monosubstitued or N,N-disubstitued(meth)acrylamides. One of thesecompounds is, for example, acrylamide.

[0072] (3)-{circumflex over (1)} N-monosubstituted (meth)acrylamides:these compounds are, for example, N-methylacrylamide, N-ethylacrylamide,N-propylacrylamide, N-butylacrylamide, N-octylacrylamide,N-phenylacrylamide, N-glycidylacrylamide, or N,N′-ethylenebisacrylamide.

[0073] (3)-{circumflex over (2)} N,N-disubstitutedmono(meth)acrylamides: these compounds are, for example,N,N-dimethylacrylamide, N-ethyl-N-methylacrylamide,N,N-diethylacrylamide, N,N-di-n-propylacrylamide, N,N-dioctylacrylamide,N,N-diphenylacrylamide, N-ethyl-N-glycidylacrylamide,N,N-diglycidylacrylamide, N-methyl-N-(4-glycidyloxybutyl)acrylamide,N-methyl-N-(5-glycidyloxypentyl)acrylamide,N-methyl-N-(6-glycidyloxyhexyl)acrylamide, N-acryloylpyrrolidine,N-acryloyl-L-proline methyl ester, N-acryloylpiperidine,N-acryloylmorpholine or 1-acryloylimidazole.

[0074] (3)-{circumflex over (3)} N,N′-disubstitutedbis(meth)acrylamides: these compounds are, for example,N,N′-diethyl-N,N′-ethylenebisacrylamide,N,N′-dimethyl-N,N′-hexamethylenebisacrylamide or(N,N′-ethylene)bisacrylamide.

[0075] (4) Vinylpyridines are, for example, vinyl or isopropenylsubstituted

[0076] pyridines such as 2-vinylpyridine, 2-isopropenylpyridine, or4-vinylpyrideine.

[0077] (5) N-substituted maleimides: these compounds are, for example,

[0078] (5)-{circumflex over (1)} N-aliphatic substituted maleimides:these compounds are, for example, N-methylmaleimide or N-ethylmaleimide.

[0079] (5)-{circumflex over (2)} N-aromatic substituted maleimides:these compounds are, for example, N-phenylmaleimide orN-(4-methylphenyl)maleimide.

[0080] (6) Vinylketones: These compounds are, for example,methylvinylketone, isopropenylmethylketone, ethylvinylketone,ethylisopropenylketone, butylvinylketone, or phenylvinylketone.

[0081] (7) Styrene derivatives: These compounds are, for example,p-methoxycarbonyl styrene, p-t-butoxycarbonylstyrene, or p-cyanostyrene.These polar unsaturated compounds may have any substituents other thanthose described above as far as they do not hinder the methods of thepresent invention.

[0082] Among these unsaturated compounds, preferable ones are, forexample, as follows:

[0083] (1)-{circumflex over (1)} Monoesters formed by esterificationbetween monohydric alcohols and acrylic acid or methacryic acid: theseesters are, for example, methyl acrylate, methyl methacrylate, ethylacrylate, propyl methacrylate, butyl acrylate, 2-ethylhexylmethacrylate, lauryl acrylate, stearyl methacrylate,1,1,1,3,3,3-hexafluoroisopropyl acrylate,1,1,1,3,3,3-hexafluoroisopropyl methacrylate, 2,2,2-trifluoroethylacrylate, 2,2,2-trifluoroethyl methacrylate,1H,1H,2H,2H-heptadecafluorodecyl acrylate, allyl acrylate, allylmethacrylate, cyclohexyl methacrylate, isophonyl acrylate, glycidylacrylate, gycidyl methacrylate, tetrahydrofurfuryl acrylate, benzylacrylate or -phenylethyl methacrylate. (1)-{circumflex over (2)}Monoesters formed by esterification between dihydric alcohols whose oneend is protected by an ether bond and acrylic acid or methacrylic acid:these esters are, for example, 2-methoxyethyl acrylate, 2-ethoxyethylmethacrylate, 2-phenoxyethyl acrylate, 2-dicyclopentenyloxyethylacrylate, 1-methoxy-2-propyl methacrylate, 3-methoxypropyl acrylate,4-ethoxybutyl methacrylate, 6-methoxyhexyl acrylate, methoxydiethyleneglycol arylate, phenoxydipropylene glycol methacrylate,ethoxytripropylene glycol methacrylate, ethoxypolyethylene glycolacrylate, or methoxypolypropylene glycol methacrylate. (1)-{circumflexover (3)} Polyesters formed by esterification between acrylic acid ormethacrylic acid and all of the hydroxyl groups of a polyhydric alcoholhaving two or more than two hydroxyl groups: these esters are, forexample, ethylene glycol diacrylate, ethylene glycol dimethacrylate,propylene glycol diacrylate, propylene glycol dimethacrylate,1,3-propanediol dimethacrylate, 1,4-butanediol diacrylate,1,6-hexanediol dimethacrylate, neopentyl glycol diacrylate, neopentylglycol dimethacrylate, diethylene glycol diacrylate, dipropylene glycoldimethacrylate, triethylene glycol dimethacrylate, tripropylene glycoldiacrylate, polyethylene glycol diacrylate, polypropylene glycoldiacrylate, polypropylene glycol dimethacrylate, and, in addition,glycerin triacrylate, glycerin trimethacrylate, pentaerythritoltetramethacrylate, dipentaerythritol hexacrylate, trimethylolpropanetriacrylate, poly(ethylene oxide)triol triacrylate, poly(propyleneoxide)triol triacrylate, or poly(propylene oxide)triol trimethacrylate.

[0084] (2) Acrylonitirle or methacrylonitrile

[0085] (3)-{circumflex over (2)} N,N-disubstitutedmono(meth)acrylamides: these compounds are, for example,N,N-dimethylacrylamide, N-ethyl-N-methylacrylamide,N,N-diethylacrylamide, N,N-di-n-propylacrylamide, N,N-dioctylacrylamide,N,N-diphenylacrylamide, N-ethyl-N-glycidylacrylamide,N,N-diglycidylacrylamide, N-methyl-N-(4-glycidyloxybutyl)acrylamide,N-methyl-N-(5-glycidyloxypentyl)acrylamide,N-methyl-N-(6-glycidyloxyhexyl)acrylamide, N-acryloylpyrrolidine,N-acryloyl-L-proline methyl ester, N-acryloylpiperidine,N-acryloylmorpholine or N-acryloylimidazole.

[0086] (4) Vinyl or isopropenyl substituted pyridines: these compoundsare, for example, 2-vinylpyridine, 2-isopropenylpyridine, or4-vinylpyrideine.

[0087] (5)-{circumflex over (2)}N-aromatic maleimides: these compoundsare, for example, N-phenylmaleimide or N-(4-methylphenyl)maleimide; and

[0088] (6) vinylketones: these compounds are, for example,methylvinylketone, isopropenylmethylketone, ethylvinylketone,ethylisopropenylketone, butylvinylketone, or phenylvinylketone.

[0089] More preferable polar unsaturated compounds as described aboveare as follows:

[0090] (1)-{circumflex over (1)} Monoesters formed by esterificationbetween monohydric alcohols and acrylic acid or methacryic acid;

[0091] (1)-{circumflex over (2)} monoesters formed by esterificationbetween dihydric alcohols whose one end is protected by an ether bondand acrylic acid or methacrylic acid;

[0092] (1)-{circumflex over (3)} polyesters formed by eserificationbetween acrylic acid or methacrylic acid and all of the hydroxyl groupsof polyhydric alcohols having two or more than two hydroxyl groups;

[0093] (2) acrylonitirle or methacrylonitrile; and

[0094] (3)-{circumflex over (2)} N,N-disubstitutedmono(meth)acrylamides.

[0095] In the present invention, the polar unsaturated compound can beused alone or in combination with two or more of them.

[0096] In case of applying plural compounds together, there may be amethod of simultaneous application, that of sequential one or that ofrepeating sequential ones. When plural monomers are polymerized togethersimultaneously, higher random copolymers are obtained depending on thereactivity of the compounds and when two or more than two monomers arepolymerized in sequential order, block polymers containing two or morethan two blocks are obtained. When repeating the simultaneous andsequential polymerization, further complicated copolymers are obtained.

[0097] In the present invention an active hydrogen compound is used aschain transfer agent when catalytic living polymerization is carriedout.

[0098] As the active hydrogen compounds there are, for example, activehydrogen compounds having active hydrogen on carbon atom, those havingactive hydrogen on oxygen atom, those having active hydrogen on nitrogenatom, or those having active hydrogen on sulfur atom. Any other activehydrogen compounds may be used as far as they do not hinder the methodsof the present invention.

[0099] Specific examples of the active hydrogen compounds having activehydrogen on carbon atom are, for example, monocarboxylates such as ethylacetate, cyclohexyl propionate, isopropyl butyrate, methyl isobutyrate,t-butyl isobutyrate, hexyl caproate, butyl laurate, methyl stearate,ethyl oleate, methyl phenylacetate, methyl cyclohexanecarboxylate,1,2-bis(2-propylcarbonyloxy)ethane, or1,2,3-tris(2-propylcarbonyloxy)propane; polycarboxylates such asdimethyl malonate, dimethyl methylmalonate, diethyl succinate, butyl2,3-dimethylsuccinate, methyl adipate, ethyl suberate, methylbutanetetracarboxylate, 1,2-bis(2-methoxycarbonylethoxy)ethane,1,2-bis(2-ethoxycarbonylpropoxy)ethane,1,2-bis(2-ethoxycarbonylpropylmercapto)ethane,N,N,N′,N′-tetrakis(2-butoxycarbonylpropyl)ethylenediamine;ketocaroxylates such as ethyl acetoacetate, cyclopentyl acetoacetate,methyl carbamoylacetate, ethyl 2-cyclohexylcarbonylacetate, or butylbenzoylacetate; nitriles such as acetonitrile, 2-cyanopropane,malononitrile, methylmalononitrile, 1,3-dicyanopropane, or adiponitrile;ketones such as acetone, methylethylketone, diisopropylketone,dicyclohexylketone, acetophenone, or isopropylphenylketone.

[0100] Specific examples of the active hydrogen compounds having activehydrogen on oxygen atom are monohydric alcohols such as methanol,ethanol, n-propanol, isopropanol, n-butyl alcohol, sec-butyl alcohol,tert-butyl alcohol, isopentyl alcohol, tert-pentyl alcohol, n-octylalcohol, lauryl alcohol, cetyl alcohol, cyclopentanol, cyclohexanol,allyl alcohol, crotyl alcohol, methylvinylcarbinol, benzyl alcohol,1-phenylethyl alcohol, triphenylcarbinol, cinnamyl alcohol,perfluoro-tert-butyl alcohol, α-hydroxyisopropylphenylketone,α-hydroxycyclohexylphenylketone, or methylα-hydroxyisobutyrate;polyhydric alcohols such as ethylene glycol, propylene glycol,diethylene glycol, dipropylene glycol, 1,3-propandiol, 1,3-butanediol,1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanediol, trimethylolpropane,glycerin, diglycerin, pentaerythritol, or dipentaerythritol; aromatichydroxy compounds such as phenol, cresol, xylenol, 2-naphthol,2,6-dihydroxynaphthalene, or bisphenol A.

[0101] Specific examples of the active hydrogen compounds having activehydrogen on nitrogen atom are aliphatic or aromatic primary amines suchas methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine,isobutylamine, sec-butylamine, tert-butylamine, cyclohexylamine,benzylamine, β-phenylethylamine, aniline, o-toluidine, m-toluidine, orp-toluidine; aliphatic or aromatic secondary amines such asdimethylamine, methylethylamine, diethylamine, di-n-propylamine,ethyl-n-butylamine, methyl-sec-butylamine, dipentylamine,dicyclohexylamine, N-methylaniline, or diphenylanmine; polyamines havingprimary or secondary amino groups such as ethylenediamine,di(2-aminoethyl)amine, hexamethylenediamine,4,4′-diaminodiphenylmethane, tri(2-aminoethyl)amine,N,N′-dimethylethylenediamine, N,N′-diethylethylenediamine, or(2-methylaminoethyl)amine; saturated cyclic secondary amines such aspyrrolidine, piperidine, morpholine, or 1,2,3,4-tetrahydroquinoline;unsaturated cyclic secondary amines such as 3-pyrroline, pyrrole,indole, carbazole, imidazole, pyrazole, or purine; cyclic polyaminescontaining secondary amino groups such as piperazine, pyrazine, or1,4,7-triazacyclononane; unsubstituted or N-monosubstituted acid amidessuch as acetoamide, propionamide, N-methylpropionamide, N-methylbenzoicacid amide, or N-ethylstearic acid amide; cyclic amides such asβ-propiolactam, 2-pyrrolidone, δ-valerolactam, or ε-caprolactam;dicarboxylic acid imides such as succinimide, maleimide, or phthalimide.

[0102] The active hydrogen compounds having active hydrogen on sulfuratom are, for example, monothiols such as methanethiol, ethanethiol,n-butanethiol, t-butanethiol, hexanethiol, decanethiol,cyclopentylmercaptane, or cyclohexylmercaptane; polythiols such as1,2-ethanedithiol, 1,3-propanedithiol, 2,3-butanedithiol,1,6-hexanedithiol, 1,2,3-propanetrithiol, or2,3-di(mercaptomethyl)-1,4-butanedithiol;aromatic mercapto compoundssuch as thiophenol, o-thiocresol, thionaphthol, or 1,2-benzenedithiol.

[0103] As further active hydrogen compounds there arepoly(alkyleneoxides) having active hydrogen at the end of the moleculesuch as polyethyleneoxide or polypropyleneoxide;(co)poly{(meth)acrylates},(co)poly{(meth)acrylonitriles},(co)poly(acrylamides), (co)poly(vinylpyridines), (co)Poly(N-sustituedmaleimides), (co)poly(vinylketones), or (co)poly(styrene derivatives)which have active hydrogen at the ends of the molecule and/or in thebackbone chain, and furthermore, (co)polyesters, (co)polyamides,(co)polylactides, and (co)polysiloxane.

[0104] The active hydrogen compounds as described above act as chaintransfer agent. Although the mechanism of the action is not necessarilyclearly understood, it might be interpreted as follows: Since theequilibrium reaction proceeds reversibly and quite rapidly between newanions generated by the addition of organic oxyanions composing organicoxysalt compounds to polar unsaturated compounds and parts having activehydrogen atoms, the active hydrogen atoms are separated as protons fromthe parts having the active hydrogen atoms and are attracted toward theanions resulting in starting of polymerization also from the parts. Thesaid active hydrogen compounds include chemical compounds having pluralnumber of active hydrogen and whether the polymerization starts from allthe parts having active hydrogen or from a part of them depends upon thedegree of dissociation of the said active hydrogen, the reactivity ofthe attracted anion, the kind of the polar unsaturated compound, or thekind of the solvent applied.

[0105] The active hydrogen compound can be used alone or in combinationof two or more of them simultaneously.

[0106] Among these active hydrogen compounds, preferable ones aremonocarboxylates such as ethyl acetate, cyclohexyl propionate, isopropylbutyrate, methyl isobutyrate, t-butyl isobutyrate, hexyl caproate, butyllaurate, methyl stearate, ethyl oleate, methyl phenyl acetate, methylcyclohexanecarboxylate, 1,2-bis(2-propylcarbonyloxy)ethane or1,2,3-tris(2-propylcarbonyloxy)propane; polycarboxylates such asdimethyl malonate, dimethyl methylmalonate, diethyl succinate, butyl2,3-dimetylsuccinate, methyl adipate, ethyl suberate, methylbutanetetracarboxylate, 1,2-bis(2-methoxycabonylethoxy)ethane,1,2-bis(2-ethoxycarbonylpropoxy)ethane,1,2-bis(2-ethoxycarbonylpropylmercapto)ethane,N,N,N′,N′-tetrakis(2-butoxycarbonylpropyl)ethylenediamine; monoalcoholssuch as methanol, ethanol, n-propanol, isopropanol, n-butyl alcohol,sec-butyl alcohol, tert-butyl alcohol, isopentyl alcohol, tert-pentylalcohol, n-octyl alcohol, lauryl alcohol, cetyl alcohol, cyclopentanol,cyclohexanol, allyl alcohol, crotyl alcohol, methylvinylcarbinol, benzylalcohol, 1-phenylethyl alcohol, triphenylcarbinol, or cinnamyl alcohol,perfluoro-tert-butyl alcohol, α-hydroxyisopropylphenylketone,α-hydroxycyclohexylphenylketone, or methylα-hydroxyisobutyrate;polyhydric alcohols such as ethylene glycol, propylene glycol,diethylene glycol, dipropylene glycol, 1,3-propandiol, 1,3-butanediol,1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanediol, trimethylolpropane,glycerin, diglycerin, pentaerythritol, or dipentaerythritol; monothiolssuch as methanethiol, ethanethiol, n-butanethiol, t-butanethiol,hexanethiol, decanethiol, cyclopentylmercaptane, orcyclohexylmercaptane; (co)poly(alkyleneoxide) having active hydrogen atthe end and/or in the backbone chain, (co)poly{(meth)acrylates},(co)poly{(meth)acrylonitriles}, (co)poly(acrylamides),(co)poly(vinylpyridines), (co)poly(N-sustitued maleimides),(co)poly(vinylketones), or (co)poly(styrene derivatives).

[0107] The modes of the polymerization of the present invention are notparticularly limited. Usually, after contacting hydroxyketone compoundor a solution of the compound prepared by dissolving in suitablesolvent, if necessary, with organic oxysalt compound, chain transferagent to be used is added, and then polar unsaturated compound iscontacted to polymerize it. If necessary, in a batch method of chargingthem together, the said unsaturated compound may also be chargedintermittently or continuously. In case of obtaining copolymers, inaccordance with the desired forms of copolymers the methods of chargingplural number of these polar unsaturated compounds all together,intermittently, or continuously or the method of charging the pluralnumber of polar unsaturated compounds in sequential order may beadopted. Quantity of the organic oxysalt compound to be used is notparticularly restricted and usually 1×10⁻⁷ to 1×10⁻¹ moles to 1 mole ofthe said polar unsaturated compound and preferably in the range of1×10⁻⁴ to 3×10⁻¹ moles. Quantity of the hydroxyketone compound to beused is usually 0.05 moles and more, preferably 0.5 to 1.50 moles, andmore preferably 0.95 to 1.05 moles to 1 mole of the organic oxysaltcompound. Quantity of the chain transfer agent, i.e., the activehydrogen compound varies. It depends on the molecular weight of the(co)polymer to be produced and usually 1×10⁻⁶ to 5×10⁻¹ moles to 1 moleof the polar unsaturated compound and preferably in the range of 1×10⁻⁴to 2×10⁻¹ moles. The temperature of the polymerization varies. Itdepends upon the organic oxysalt compound, hydroxyketone compound, thechain transfer agent to be used, and the kinds and quantity of the saidpolar unsaturated compound. It is usually −50° C. to 250° C., preferablyin the range of −20° C. to 150° C. The pressure of the polymerizationvaries. It depends on the kinds, quantity, and the reaction temperature,and is usually below 3.0 MPa (absolute pressure in mega pascal, the samein the following), preferably 0.01 to 1.5 MPa, more preferably 0.1 to1.0 MPa.

[0108] The reaction time required for the polymerization depends on theorganic oxysalt compound and the hydroxyketone compound which are used,the kinds and quantity of the chain transfer agent to be used and thesaid polar unsaturated compound. The reaction temperature is usuallywithin 50 hours and preferably 0.1 to 24 hours.

[0109] Usually the said polar unsaturated compound contains a trace of apolymerization inhibitor, however in the method of the present inventionthe polymerization may be carried out in the presence of thepolymerization inhibitor.

[0110] The polymerization in the method of the present invention may becarried out in a molten state of the said polar unsaturated compound. Ifnecessary, suitable solvent may also be used. The polymerization mayproceed in homogeneous solution or in suspension. The solvent is, forexample, aliphatic or alicyclic hydrocarbon such as n-hexane, n-heptane,or cyclohexane; aromatic hydrocarbon such as benzene, toluene, orxylene; aromatic halogenated aromatic compound such as chlorobenzene ordichlorobenzene; ether such as diethyl ether, diphenylether,tetrahydrofuran, tetrahydropyran, 1,4-dioxane, ethylene glycol deimethylether, or diethylene glycol diethyl ether; aprotic polar solvent such asdimethylformamide, dimethyl sulfoxide, sulfolane, orN,N′-dimethylimidazolidinone. Any other solvents may be adopted as faras they do not hinder the methods of the present invention.

[0111] The cation, which formed organic oxysalt compound, remains at allor a part of a growth end of the product (co)polymer as counter ion whenthe polymerization is ended. For the purpose of separating out the(co)polymer stably, the polymerization may be terminated by addinginorganic acid such as hydrochloric acid, sulfuric acid, or phosphoricacid or organic acid such as acetic acid, propionic acid,benzenesulfonic acid, or paratoluenesulfonic acid and convert the saidcation to the salt of inorganic or organic acid. The produced(co)polymer may be used, for the next purposes, as it is, or may be usedfor the next purposes, after the termination of the polymerization, byonly solidifying the product by distilling out the solvent used, whennecessary; however usually it is possible to separate out the(co)polymer by precipitating method of adding the reaction liquid itselfor the solution wherein the dry solid is dissolved in suitable solventto poor solvent. It is also possible to purify the (co)polymer byrepeating the precipitating method.

[0112] The third invention obtained by the method of the presentinvention, that is, thermosetting powder coating composition made of the(co)polymer(A) obtained by the method of the present invention will beexplained.

[0113] As (co)polymer(A), (co)polymer of one or more kinds of polarunsaturated compound containing epoxy group obtained by the method asdescribed in any one of [1] to [12] or (co)polymer of the said polarunsaturated compound containing epoxy group and polar unsaturatedcompound is used.

[0114] As polar unsaturated compound containing epoxy group, anyunsaturated compound may be used without particular limitation as far asit contains epoxy group and typical examples of the compound are polarunsaturated compound containing epoxy group such as glycidylmethacrylate, glycidyl acrylate, β-methylglycidyl methacrylate,β-methylglycidyl acrylate, acrylglycidyl ether and one kind orcombination of two or more than two kinds of these compounds may beused.

[0115] As polar unsaturated compound which may be copolymerized withpolar unsaturated compound containing epoxy group there is no particularlimitation as far as polar unsaturated compound is concerned, and thetypical examples of the compound are monomers of acrylates ormethacrylates having alkyl or cyclohexyl group having 1 to 14 carbons,for example, acrylic acid derivatives or methacrylic acid derivativesincluding methyl-, ethyl-, n-propyl-, isopropyl-, n-butyl-, isobutyl-,n-amyl-, isoamyl-, n-hexyl-, cyclohexyl-, 2-ethylhexyl-, octyl-,2-ethyloctyl-, decyl-, dodecyl-, and cyclohexyl-acrylates ormethacrylates, and one kind or mixture and combination of two or morethan two kinds of these compounds may be used.

[0116] As other specific examples of the polar unsaturated compound,there are other ethylenic unsaturated monomers, for example, aromaticvinyl compounds such as styrene,α-methylstyrene and vinyltoluene;dicarboxylates such as maleic acid and itaconic acid; unsaturatedmonomers of ethylene halides such as vinyl chloride, vinylidenechloride, vinyl fluoride, monochlorotrifluoroetylene,tetrafluoroethylene, chloroprene; nitriles such as acrylonitrile andmethacrylonitrile; vinyl esters such as vinyl acetate and vinylpropionate; α-olefines such as ethylene, propylene, isoprene, butadiene,α-olefines having 4 to 20 carbon atoms; alkylvinyl ethers such aslaurylvinyl ether; vinyl compounds containing nitrogen such asvinylpyrrolidone and 4-vinylpyrrolidone; one kind or mixture andcombination of two or more than two kinds of these monomers may be used.

[0117] In the method of the present invention, content of the polarunsaturated compound containing epoxy group in the (co)polymer(A) is 15to 100 mole %, preferably 20 to 60 mole % of the total monomers.

[0118] In the light of storage stability of the powder coatingcomposition and surface flatness of the paint film caused by reductionin fluidity of the coating composition during the baking of thecoatings, the glass transition temperature of the (co)polymer(A) ispreferably 10 to 100° C., more preferably, 20 to 70° C. Better storagestability is obtained when the glass transition temperature is above 10°C. and preferable melt viscosity is obtained resulting in betterexternal appearance of paint film when it is below 100° C.

[0119] In the present invention the glass transition temperature ismeasured using robot DSC RDC220 (Seikou Denshi Kougyou's product) at 10°C./min. from −20 to 120° C. The definition of the glass transitiontemperature is described in page 131 of Koubunshi Jiten (KoubunshiGakkai Henshuu, Asakura Shoten Hakkou, Shouwa 46 Nen Shohan)

[0120] As the curing agent composition component (B), which can cure the(co)polymer(A) as described above, to be used for the thermosettingpowder coating composition of the present invention, the compounds whichcan cure the (co)polymer(A) by reacting with the functional groups inthe (co)polymer(A) are used. However when the said functional group isepoxy, at least one kind of compound selected from the group consistingof polycarboxylic acid and/or polycarboxylic acid anhydride ispreferable. The compound is the component of the composition of curingagent which reacts with the epoxy groups existing in the molecule of thecomposition of resin to be used for the powder coatings of the presentinvention.

[0121] As the compound of polycarboxlic acid any aliphatic, aromatic,and alicyclic compound may be used. Specific examples of the aromaicpolycarboxylic acids are isophthalic acid and trimellitic acid and theseacids may be used as single or the combination of them. Specificexamples of the alicyclic polycarboxylic acids are hexahydrophthalicacid and tetrahydrophthaic acid and these acids may be used as single orthe combination of them. Polyester resin having carboxyl group may beused also. However, in the present invention the compound of aliphaticpolycarboxylic acid is preferably used in the light of the paint filmproperty such as the surface flatness and the weather resistance.

[0122] There is no particular limitation regarding the aliphaticpolycarboxylic acid (b-1) as far as it is aliphatic compound havingsubstantially at least 2 carboxylic groups in the molecule and one ormore than one kinds of the aliphatic compound may be used.

[0123] Specific examples of the aliphatic polycarboxylic acid (b-1) arealiphatic dicarboxylic acid. As specific examples of the aliphaticdicarboxylic acid are those having carbon number of around 4 to 24 suchas succinic acid, glutaric acid, adipic acid, pimelic acid, subericacid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioicacid, brassilic acid, octadecanedioic acid, and eicosanedioic acid, andthe dodecanedioic acid is preferable among them and these acids are usedsingly or in combination of them.

[0124] The polycarboxylic acid anhydride (b-2) in the present inventionis not particularly limited as far as the acid anhydride is a compoundwhich contain aliphatic acid anhydrides of linear oligomer of more thandimmers or polymers substantially having or not having carboxyl groupsin the molecule and have at least 2 carboxyl groups and/or acidanhydride groups existing substantially in the molecules, and one ormore than one kinds of the polycarboxylic acid anhydrides may be used.An example of the polycarboxylic acid anhydride is a dehydrationcondensation product of the polycarboxylic acid (b-1). Among them linearcondensed anhydride of dodecandioic acid is preferable and its typicalexample is Additol XVL1381 (Sorushia's product). The polycarboxylic acidanhydride (b-2) is preferably prepared so that the melting point is inthe range of 40 to 150° C.

[0125] In the method of the present invention various additives can beadded which are usually added to coatings. The external appearance orthe paint film property may also be improved by adequate blendingsynthetic resin composition containing epoxy resin, polyester resin, orpolyamide, natural resin or semi-synthetic resin composition containingcellulose or cellulose derivatives with the thermosetting powder coatingcomposition of the present invention depending on the purpose of use.

[0126] Additives such as curing catalyst, pigment, fluidity adjustingagent, thixotropy agent (thixotropy adjusting agent), antistaic agent,surface adjusting agent, luster agent, blocking preventing agent,plasticizer, ultraviolet absorbing agent, blowing preventing agent, andslip agent may be adequately blended with the thermosetting powdercoating composition of the present invention depending on the purpose ofuse. In the case of using as clear coat, coloring may be operated byblending a small amount of pigment so that complete hiding property doesnot occur.

[0127] When composition containing (co)polymer(A) and component (B) arekneaded mechanically, the mixing temperature is not limited particularlyas far as substantially homogeneous composition of the powder coatingcan be prepared. Heating roller, heating kneader, or extruder is usuallyused as apparatus for kneading by melting.

[0128] As a specific example of the methods for blending the compositionof the thermosetting powder coating composition of the presentinvention, a method of adequate combination of kneader and blender suchas roller, kneading machine, mixer (Vanvary type and Transfer type),calender, or extruder for sufficiently homogeneous mixing at eachprocess condition adequately chosen (temperature, melting or nonmelting,r.p.m., vacuum atmosphere, and inert atmosphere) may be adopted, andthen, a method of obtaining homogeneous fine powders of the compositionsof powder coatings by pulverizers may be adopted, however these methodsare not particularly limited and there may be other methods than thoseas described above.

[0129] Block of the coating composition obtained by the blending iscooled down, and then is pulverized so that the mean particle diameterbecomes 10 to 90 μm. As pulverizers hammer mills are used.

[0130] The thermosetting powder coating composition obtained by thepulverization is adhered to the surface of the objects to be coated by amethod of electrostatic coating or fluidized bed one and paint film isformed by thermosetting the composition by heating. In case of theprocess of baking the thermosetting powder coating composition of thepresent invention, it is possible to carry out crosslinking reactionbetween the (co)polymer(A) and the curing agent composition component(B) usually at a temperature of about 100° C. to 180° C., morepreferably, about 120° C. to 160° C., normally for about 10 min. to 60min. After the baking process, paint film having excellent property isobtained by cooling to the room temperature.

[0131] When the thermosetting powder coating composition of the presentinvention is used as top coating and not only conventional type coatingsbut also water borne coatings are used as under coating, the paint filmof the coating composition of the present invention after the bakingprocess has as excellent property as in case of using solvent typecoatings.

[0132] That is, after under coatings (including those containingpigments and/or metal powders) are painted and dried for certain hours,in accordance with the method as described above the thermosettingpowder coating composition of the present invention is adhered to thesurface of the under coatings and the paint film is formed bythermosetting the composition by heating.

[0133] The painting method of the thermosetting powder coatingcomposition related to the present invention are applied to automobilebodies or parts of the automobiles (aluminum wheel, windshield wiper, orcenter pillar).

[0134] The paint film formed by an appropriate or public known or publicuse painting method has excellent property with regard to storagestability (blocking resistance), external appearance (surface flatness,brightness, and transparency), physical property (hardness, scratchresistance, and adhesion property of top coating), and chemical property(weather resistance, acid resistance, and solvent resistance).

EXAMPLE

[0135] The present invention is explained by the following examples inmore detail, however these examples are not limiting and should beinterpreted only as for explanation.

Example 1

[0136] After a 300 ml flask equipped with a stirrer, a dropping funnel,and a tube for temperature measurement was dried sufficiently,2-hydroxy-2,4,4-trimethyl-3-pentanone (169 mg,1.17 mmol) was weighedaccurately and transferred into the flask, and a tetrahydrofuran(abbreviated as THF hereinafter) solution (11.7 ml, 1.17 mmol)containing tetraphenylphosphoniummethoxide (0.10 M) was added to it andstirred to obtain a homogeneous solution. N-butanol (87 mg, 1.17 mmol)as a chain transfer agent was added to the solution and further a THFsolution (176 ml, containing MMA 35.1g 351 mmol)of methyl methacrylate(abbreviated as MMA)(2.00 M) was dropped so that the reactiontemperature did not exceed 50° C. It took about 30 min. to drop thesolution. After the dropping was completed, the solution was stirred for3 hours and then a THF solution (2.00 ml, 2.00 mmol) of acetic acid (1.0M) was added and the reaction was stopped. A small amount of thereaction mixture was taken and quantitative analysis was carried out bygas chromatography using 1,3,5-trichlorobenzene as an internal standard.As a result of the analysis, the methyl methacrylate and the n-butanolwere completely consumed. The remaining reaction mixture except for 0.5ml to be used for GPC analysis was poured into methanol (about 2 L).Precipitated solid was separated by filtration and washed 3 times withmethanol (40 ml). The obtained solid was dried for 6 hours at 50° C.under 10 mmHg and odorless solid (34.2 g) was obtained. ¹-NMR and¹³C-NMR spectrum of the solid was almost identical with the poly(methylmethacrylate)of Aldrich Company's product. A solution was prepared sothat the concentration of the poly(methyl methacrylate) became about 0.5wt % by diluting the remaining reaction mixture (0.5 ml) with THF andGPC analysis with standard polymer of poly(methyl methacrylate) wascarried out by means of GPC column(Product of Showa Denkou Co.,connected with 2 columns shodex-KF-803L and shodex-KF-804L)and using THFas developing solvent. As a result of the analysis, the number averagemolecular weight of the obtained poly(methyl methacrylate) was 14,800,while the theoretical number average molecular weight was 15,100 whichwas calculated from the calculating formula(2) of the present inventionand these two figures are quite similar. Furthermore, the molecularweight distribution index (M_(w)/M_(n)) was 1.11, i.e., the distributionis quite narrow, therefore the polymer was found to be monodispersive.The result obtained means that two polymer molecules having similarnumber average molecular weight were produced per one molecule ofcatalyst component.

Examples 2-6

[0137] For the purpose of further confirming the property of catalyticliving polymerization of MMA, the same polymerizations as in Example 1were carried out except for changing the amounts of the chain transferagent n-butanol. In every case, n-butanol and MMA were completelyconsumed. The results of GPC analysis of the obtained poly(methylmethacrylates) are shown in Table 1 with that of Example 1. The numberaverage molecular weights of polymers obtained in each Example are quiteagreeable with those of the theoretical number average molecularweights. The deviation from the theoretical number average molecularweights was within 3% of the theoretical ones. Furthermore, themolecular weight distribution indexes of the polymers obtained were1.06-1.18 which means the polymers were monodispersive ones. The seriesof these results indicate strongly that polymerization of MMA usingorganic oxysalt compounds as catalysts in the presence ofhydroxycarbonyl compounds having at least both alcoholic hydroxyl groupsand carbonyl groups in the same molecules proceeds by the catalyticliving polymerization.

Comparative Example 1

[0138] The same polymerization as in Example 1 was carried out exceptfor not using 2-hydroxy-2,4,4-trimethyl-3-pentanone. The consumptionrates of n-butanol and MMA were 78% and 100%, respectively. The obtainedpolymer was the mixture of the polymers having number average molecularweights of 41,600 and 8,000 and the molecular weight distribution indexwas 4.61. This result and the result obtained in the Example 1 indicatethat hydroxyketone compound plays a very important role in the controlof the polymerization. TABLE 1 Amount of Results of GPC n-butanol usedTheoretical Analysis Example mmol Mn Mn Mw/Mn 1 1.17 15,100 14,800 1.112 2.34 10,100 9,900 1.18 3 4.68 6,070 6,010 1.16 4 10.5 3,080 2,990 1.095 22.2 1,570 1,600 1.09 6 23.9 1,100 1,070 1.06

Application Example

[0139] “Part” and “%” in the following explanation are the values basedon mass, if not described otherwise.

[0140] [Preparation of Painting Plates]

[0141] White coating material of acrylic-melamine crosslinking waspainted with thickness of 20 μm on a bonderite steel plate havingthickness of 0.8 mm which has already been treated with zinc phosphate.The steel plate was then baked at 140° C. for 30 min and substratecoated steel plate was prepared.

[0142] [Performance Evaluation]

[0143] The performance evaluation was made according to the followingmethods:

[0144] {circumflex over (1)} Blocking Resistance Test of Powder CoatingComposition

[0145] After storing powder coating composition (6.0 g) for 7 days at23° C. in a cylindrical container having 20 mm inner diameter, thepowder coating composition was taken out and the degree of blocking ofthe powder coating composition was evaluated according to ⊚,◯, and X byeye-observation and contact with fingers.

[0146] ⊚: quite normal

[0147] ◯: poor a little bit

[0148] X: poor

[0149] {circumflex over (2)} External Appearance by Eye-Observation(Surface Flatness, Brightness)

[0150] External appearances of paint film was evaluated byeye-observation according to ⊚,◯, and X.

[0151] ⊚: particularly excellent

[0152] ◯: good

[0153] X: poor

[0154] {circumflex over (3)} Long Wave(Lw)

[0155] Lw was measured by Wave-scan-plus (BYK company's product). The Lwis an index indicating the surface flatness of paint film.The less theindex value is, the more smooth the surface is.

[0156] {circumflex over (4)} Luster

[0157] Measured values by a glossmeter (60° gloss) were indicated.

[0158] {circumflex over (5)} Transparency

[0159] Color difference(ΔE) between the paint films to be measured andthose of substrate coating was measured by a Color guide (BYK company'sproduct).

[0160] ⊚: −0.5<ΔE<0.5

[0161] X : ΔE≦−0.5 or 0.5≦ΔE

[0162] {circumflex over (6)} Hardness Test of the Paint Films

[0163] The pencil hardness test (based on Japanese Industrial Standards:JIS K5400 6.14) was applied to evaluate the hardness. The indication wasexpressed by pencil hardness symbols.

[0164] {circumflex over (7)} Scratch Resistance

[0165] Scratching test of rubbing the surface of the paint film by abrush using a 3% solution of abrasive compound suspension was carriedout and luster retention rate was calculated by the evaluation of luster(20° gloss) before and after the rubbing.

Luster retention rate=(20° gloss after the test)/(200 gloss before thetest)×100

[0166] The luster retention rate was evaluated according to ⊚,◯, and X.

[0167] ⊚: 60% and more

[0168] ◯: 40% and more, less than 60%

[0169] X: less than 40%

[0170] {circumflex over (8)} Recoating Property

[0171] The test of the recoating property was carried out by thecross-cut adhesion test based on JIS K5400 8.5.2. The number of unpeeledparts was evaluated according to ⊚,◯, and X.

[0172] ⊚: 100

[0173] ◯: 80 and more, less than 99

[0174] X: less than 80

[0175] {circumflex over (9)} Acid Resistance

[0176] A 10 vol. % solution of sulfuric acid was dropped on the surfaceof the paint film and it was left alone at room temperature for one day.Then, the sulfuric acid solution was wiped off and the surface wasevaluated according to ⊚,◯, and X by observation of external appearance.

[0177] ⊚: No scars were found.

[0178] ◯: Very few scars were observed.

[0179] X: Scars were observed.

[0180] {circumflex over (10)} Solvent Resistance

[0181] After rubbing the surface of paint film with a gauze impregnatedwith xylol for 50 times of reciprocation, the surface was evaluated byobservation according to ⊚,◯, and X.

[0182] ⊚: No scars were found.

[0183] ◯: Very few scars were observed.

[0184] X: Scars were observed.

[0185] {circumflex over (11)} Weatherability Test

[0186] Acceleration test was carried out according to QSWOM for 2000hours and luster of the paint film before and after the test wasmeasured and the retention rate of luster(%) was calculated by thefollowing formula:

Retention rate of luster=(20° gloss after the acceleration test)/(20°gloss before the acceleration test)×100

[Polymer (A) Production Example 1]

[0187] The (co)polymer (A) of the present invention was evaluated ascoating resin.

Example 7 (Production Example 1)

[0188] After a 10 L flask equipped with a stirrer, a dropping funnel,and a tube for temperature measurement was dried sufficiently,hydroxyketone compound, i.e., 1-hydroxycyclohexylphenylketone (5.37 g,26.3 mmol) and oxysalt compound, i.e., potassium salt of diethylmethylmalonate (5.33 g, 25.1 mmol) were weighed accurately undernitrogen atmosphere at room temperature and transferred into the flask.THF (1400 ml) was added to them and stirred to obtain a homogeneoussolution. Methyl isobutyrate (12.8 g, 126 mmol) as chain transfer agentwas added to the solution. Then, the solution was cooled with ice. Tothe solution was dropped a 1256 ml THF solution wherein MMA (1.00 M),n-butyl methacrylate (hereinafter abbreviated as n-BMA,0.1 M), isobutylmethacrylate (hereinafter abbreviated as i-BMA, 0.1M) and glycidylmethacrylate (hereinafter abbreviated as GMA, 0.8 M) are containedrespectively (containing 126 g : 1.26 mol MMA, 17.9 g 126 mmol n-BMA,17.9 g : 126 mmol i-BMA, 143 g : 1.00 mmol GMA) so that the reactiontemperature did not exceed 10° C. The time required for the dropping wasabout 2 hours. After the dropping was completed, the solution wasstirred for further 5 hours at room temperature and then, the reactionwas stopped by adding THF solution (46.5 ml, 46.5 mmol) of 1.0 M aceticacid. All of the monomers had been consumed completely. Aluminiumsilicate (25.6 g) was added to the reaction mixture and the mixture wasstirred for 2 hours at room temperature and filtered. The mother liquorwas concentrated to solidify it and the obtained solid was dried at 50°C. under 10 mmHg for 24 hours. 297 g of colorless and odorless solid wasobtained. The glass transition temperature of the solid was 35° C. andthe number average molecular weight of the obtained copolymer was 2,410while its theoretical number average molecular weight was 2,138 and itsmolecular weight distribution index was 1.34.

[Related Comparative Production Example of (co)polymer(A)]

[0189] A flask having 4 inlets equipped with a stirrer, a thermometer, areflux condenser, and an inlet for introducing nitrogen was charged with66.7 parts of xylene and heated to the temperature of refluxing. Polarunsaturated compound (parts) and t-butylperoxy 2-ethylhexanoate (PB-O:Nihon Yushi's product) as polymerization initiator as indicated in Table2 were dissolve in the xylene and the mixed solution was dropped during5 hours and was kept at 100° C. for 5 hours thereafter. Polymers(Comparative Production Examples 1,2,and 3) were obtained by removingthe solvent of the polymer solution which had been produced. Thecharacteristics of the copolymers obtained are also indicated in theTable 2. TABLE 2 Production Example 1 and Comparative ProductionExamples 1, 2 and 3 Comparative Comparative Comparative ProductionProduction Production Production Example 1 Example 1 Example 2 Example 3Methyl 50 50 35 35 methacrylate n-butyl 5 5 5 5 methacrylate Isobutyl 55 5 5 methacrylate Glycidyl 40 40 40 40 methacrylate Styrene — — 15 15PB-O *1 — 10 8 13 Number 2410 2480 2300 1720 average molecular weight(Mn) Weight 3220 5780 5150 3510 average molecular weight (Mw) Molecular1.34 2.33 2.24 2.04 weight distribution (Mw/Mn) Glass 35 35 35 20transition temperature (° C.)

[Application Examples 1 and 2]

[0190] Weight ratios (parts) indicated in Table 2 ofpolymer(A)(Production Example 1) and curing agent compositioncomponent(B) were blended and 1.5 parts of CGL1545 (Chiba GaigyCompany's product, ultraviolet absorbing agent), 1.5 parts of Chinubin144 (Chiba Gaigy Company's product, light stabilizer), 0.2 parts ofbenzoin (blowing preventing agent), 0.5 parts of ethylenebisstearoamide(blowing preventing agent and slip agent), and 1.0 part of Resimix RL-4(fluidity adjusting agent) were added to the total 100 weight parts of(A) and (B), and after the mixture as described above was kneaded inmolten state in a kneading machine and cooled, it was pulverized by apulverizer and powder coating was obtained. After the produced powdercoating was painted on the substrate coated steel plate by theelectrostatic spray so that the paint film thickness became 40 μm, testplate for adhesion test of the top coating was obtained by heating thesteel plate at 150° C. for 30 min.

[Application Comparative Example 1, 2, 3, and 4]

[0191] Except that Application Comparative Polymer ((A) ApplicationComparative Production Examples 1, 2, and 3) and (B) were blended in theratio as indicated in Table 3, test plate was obtained according to thesame method as in the Application Example 1.

[Evaluation results of Application Examples and Comparative Examples]

[0192] Evaluation results of the powder coatings and the paint filmsformed in Application Examples 1 and 2 are shown in Tables 3 and 4.Evaluation results of the powder coatings and the paint films formed inApplication Comparative Examples 1, 2, 3, and 4 relating to theApplication Examples 1 and 2 are also shown in Tables 3 and 4. Thepowder coatings compositions of the Examples as indicated in Table 4 arewithin the scope of the present invention and the results shown in thetable indicate that the compositions of the present invention are thethermosetting powder coatings compositions which can provides the paintfilms having external appearance (surface flatness, brightness, andtransparency), physical property (hardness, scratch resistance, andrecoating property), and chemical property (weather resistance, acidresistance, and solvent resistance) without lowering the storagestability(blocking resistance) as compared to the conventional powdercoatings. TABLE 3 Coating compositions of Application Examples 1,2 andApplication Comparative Examples 1,2,3, and 4 Application ApplicationApplication Application Application Application Comparative ComparativeComparative Comparative Example Example Example Example Example Example1 2 1 2 3 4 Polymer(A) Production 76.8 68.8 Example 1 ComparativeComparative 76.8 Polymer Porduction Example 1 Comparative 76.8 68.8 68.8Production Example 2 Hardening Dodecanedioic 23.2 23.2 23.2 agent (B)acid VXL1381*² 31.2 31.2 31.2

[0193] TABLE 4 Evaluation Results of Application Examples andApplication Comparative Examples Application Application ApplicationApplication Application Application Comparative Comparative ComparativeComparative Example Example Example Example Example Example 1 2 1 2 3 4Blocking ⊚ ⊚ ◯ ◯ ◯ X resistance Visual ⊚ ⊚ X X X ◯ external appearanceLong wave 3.4 1.9 10.1 12.1 8.9 5.4 Luster 91 91 91 92 92 92 (60° gloss)Transparency ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ Paint film H H H H H B hardness Scratch ⊚ ⊚ ⊚ ⊚⊚ X resistance Recoating ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ property Acid ⊚ ⊚ ⊚ ⊚ ⊚ ◯resistance Solvent ⊚ ⊚ ⊚ ⊚ ⊚ X resistance Weather 95 95 95 93 93 66resistance

INDUSTRIAL APPLICABILITY

[0194] According to the methods of the present invention, by usinghydroxycarbonyl compounds with inexpensive organic oxysalt compoundwhich has not any particular problem at handling, it is possible toimprove to a great extent the polymerization performance of the saidorganic oxysalt compound to polar unsaturated compound. Furthermore, bypolymerization of polar unsaturated compounds using organic oxysaltcompound as catalyst in the presence of hydroxycarbonyl compound havingat least both an alcoholic hydroxyl group and a carbonyl group in thesame molecule, it is possible to produce quite effectively polymerswhose number average molecular weight and number of produced moleculesare controlled very accurately.

[0195] The present invention relates to the thermosetting powder coatingcomposition (for example, acrylic thermosetting powder coatingcomposition) having storage stability, external appearance property,physical property, and chemical property, which have not been achievedyet by the prior arts, and particularly provide thermosetting powdercoating composition (for example acrylic thermosetting powder coatingcomposition) which is particularly applied preferably to the painting,more particularly, to the painting of top coating of automobile bodiesand parts for vehicles such as automobiles (aluminum wheel, windshieldwiper, pillar, door handle, fender, bonnet, air spoiler, stabilizer, andfront grill).

1. A method of producing a living polymerized (co)polymer which methodcomprises polymerization of polar unsaturated compound in the presenceof a hydroxycarbonyl compound having at least both an alcoholic hydroxylgroup and a carbonyl group in the same molecule using an organic oxysaltcompound as catalyst.
 2. The method as claimed in claim 1, wherein acation forming the organic oxysalt compound is an alkali metal cation, atetraalkylammonium cation, a trialkylsulfonium cation, atetraarylphosphonium cation, a hexaarylphosphoranilidene ammoniumcation, or a tetrakis{tris(dialkylamino)phosphoranilideneamino}phosphonium cation.
 3. The method as claimed in claim 1, wherein a cationforming the organic oxysalt compound is a tetraalkylammonium cation, atetraarylphosphonium cation, or a hexaarylphosphoranilidene ammoniumcation.
 4. The method as claimed in any one of claims 1 to 3, wherein ananion forming the organic oxysalt compound is an organic oxyanionderived from a monohydric alcohol, an organic oxyanion derived from amonocarboxylate, or an organic oxyanion derived from a polycarboxylate.5. The method as claimed in any one of claims 1 to 3, wherein an anionforming the organic oxysalt compound is an organic oxyanion derived froma monohydric alcohol.
 6. The method as claimed in any one of claims 1 to5, wherein the hydroxycarbonyl compound is an α-hydroxyketone or anα-hydroxycarboxylate.
 7. The method as claimed in any one of claims 1 to6, wherein the polar unsaturated compound is a chemical compound havingboth a polar functional group selected from carbonyl, cyano, or pyridylgroups, and an unsaturated group in the same molecule and, in addition,the functional group and the unsaturated group form a directly orindirectly conjugated system.
 8. The method as claimed in any one ofclaims 1 to 6, wherein the polar unsaturated compound is a(meth)acrylate, a (meth)acrylonitrile, a (meth)acrylamide, avinylpiridine, a N-substitued maleimide, a vinylketone, or a styrenederivative.
 9. The method as claimed in any one of claims 1 to 6,wherein the polar unsaturated compound is a monoester between amonohydric alcohol and acrylic acid or methacrylic acid, a monoesterbetween acrylic acid or methacrylic acid and a dihydric alcohol one endof which is protected by ether linkage, a polyesters formed byesterification between acrylic acid or methacrylic acid and all of thehydroxyl groups of the polyhydric alcohol having two or more hydroxylgroups, an acrylonitrile, a methacrylonitrile, a N,N-disubstitutedmono(meth)acrylamide, a pyridine substituted by vinyl or isopropenylgroup, a N-aromatic substituted maleimde or a vinylketone.
 10. Themethod as claimed in any one of claims 1 to 9, wherein an activehydrogen compound is used as chain transfer agent.
 11. The method asclaimed in any one of claims 1 to 9, wherein the chain transfer agent isa monocarboxylate, a polycarboxylate, a monohydric alcohol, a polyhydricalcohol, a monothiol, a (co)poly(alkyleneoxides) having an activehydrogen at its end and/or in its backbone chain, a(co)poly{(meth)acrylate}, a (co)poly{(meth)acrylonitrile}, a(co)poly(acrylamide), a (co)poly(vinylpyridine), a (co)poly(N-substituedmaleimide), a(co)poly(vinylketone), or a (co)poly(styrene derivatives).12. The method as claimed in any one of claims 1 to 11, wherein thecopolymer is produced by using at least two or more of the polarunsaturated compounds together.
 13. A thermosetting powder coatingcomposition comprising; a living polymerized (co)polymer (A) obtained bythe method as claimed in any one of claims 1 to 12 and a curing agentcomposition component (B) which can cure said (co)polymer.
 14. Thethermosetting powder coating composition as claimed in claim 13, whereinthe (co)polymer(A) comprises an epoxy group.
 15. The thermosettingpowder coating composition as claimed in claim 13 or 14, wherein the(co)polymer(A) has a glass transition temperature of 10° C.-100° C. 16.The thermosetting powder coating composition as claimed in any one ofclaims 13 to 15, wherein the curing agent composition component (B)which can cure the (co)polymer comprising; (b-1) a polycarboxylic acidand/or (b-2) a polycarboxylic acid anhydride.
 17. The thermosettingpowder coating composition as claimed in any one of claims 13 to 16wherein the thermosetting powder coating composition is for use as topcoating of automobiles.